EP0702066B1 - Kugelschreiber und nicht-wässrige Tinte für Kugelschreiber - Google Patents

Kugelschreiber und nicht-wässrige Tinte für Kugelschreiber Download PDF

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Publication number
EP0702066B1
EP0702066B1 EP95114539A EP95114539A EP0702066B1 EP 0702066 B1 EP0702066 B1 EP 0702066B1 EP 95114539 A EP95114539 A EP 95114539A EP 95114539 A EP95114539 A EP 95114539A EP 0702066 B1 EP0702066 B1 EP 0702066B1
Authority
EP
European Patent Office
Prior art keywords
ink
solvent
ball point
mmhg
point pen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95114539A
Other languages
English (en)
French (fr)
Other versions
EP0702066A3 (de
EP0702066A2 (de
Inventor
Takahiro Osada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Pencil Co Ltd
Original Assignee
Mitsubishi Pencil Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP6222102A external-priority patent/JPH0885772A/ja
Priority claimed from JP7202211A external-priority patent/JPH0948941A/ja
Application filed by Mitsubishi Pencil Co Ltd filed Critical Mitsubishi Pencil Co Ltd
Publication of EP0702066A2 publication Critical patent/EP0702066A2/de
Publication of EP0702066A3 publication Critical patent/EP0702066A3/de
Application granted granted Critical
Publication of EP0702066B1 publication Critical patent/EP0702066B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K7/00—Ball-point pens
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • C09D11/18—Writing inks specially adapted for ball-point writing instruments

Definitions

  • the present invention relates to an ink for a ball point pen and a type of a ball point pen for directly reserving the ink in a ink tank or tube (thereinafter refered to as "the direct ink reserving type ball point pen").
  • JP-A-6-247091 has disclosed a method in which the outer periphery of the tip holder is also coated with a water-repellent or an oil-repellent material so as to inhibit the ink from adhering to the outer periphery of the tip holder.
  • the resultant coating material is peeled off by friction with a writing material such as a paper during writing, so that there is a tendency that the blobbing phenomenon gradually begins to occur.
  • This principle is that the critical surface tension on the outer periphery of the tip holder is decreased so as to be lower than the surface tension of the ink, thereby controlling the wetness of the ink.
  • a ink originally has the low surface tension, the surface of a high-energy material such as a metal is wetted with the ink inconveniently. Then, the non-aqueous ink is easier to wet the metal than an aqueous ink.
  • the wear of the tip by the rotation of the ball is relatively low, because the ink has a viscosity of thousands to millions cps.
  • the viscosity of the ink is less than thousands cps, the improvement of lubrication by viscous properties cannot be expected, so that the tip is extremely worn, with the result that the starving of written lines or writing impossibility takes place.
  • the ink contains a solvent having a low vapor pressure as a main component, and therefore, even if a cap is removed and a pen point is exposed to air, the starving or writing impossibility scarcely occurs.
  • the ink has a high viscosity of thousands to about one million mPa ⁇ s, a high writing pressure is required, so that writing feeling is heavy. In consequence, the fingers, arm and shoulder of a writer are easily tired by the writing for a long period of time.
  • the ink has a low viscosity, and therefore the writing feeling is light, but the main solvent is water which easily vaporizes. Therefore, if the cap is removed and the pen point is exposed to air, the starving or writing impossibility occurs inconveniently.
  • JP-A-1-299880 has disclosed a non-aqueous ink for a ball point pen in which the surface tension of an organic solvent is regulated and which has an ink viscosity of 50 to 2000 mPa ⁇ s (25°C) and simultaneously possesses the characteristics of the non-aqueous ink and the aqueous ink, but this kind of ink is not always satisfactory.
  • some aqueous inks having a middle viscosity are on the market as inks having many advantageous features from the viewpoints of quality and economy, but these inks are poorer, than the non-aqueous ink, in a cap-off performance that the writing impossibility scarcely occurs even when the cap is removed.
  • the present invention has been intended to solve the above-mentioned problems, and an object of the present invention is to provide a non-aqueous ink for a ball point pen simultaneously having the feature of the non-aqueous ink, i.e., excellence in the so-called cap-off performance that a writing performance scarcely deteriorates even when a cap is removed, and the feature of an aqueous ink that writing can be done at a low writing pressure and no blobbing occurs.
  • Fig. 1 is a view in which pen points of a ball point pen before and after writing are compared with each other.
  • the autolyophobic vehicle is adsorbed on a solid-liquid interface when the respective molecules of constitutional components or certain molecules contact with a high-energy surface, thereby lowering the critical surface tension of the solid, so that a low-energy surface is made to prevent the molecules from spreading on the surface of the solid and to thereby inhibit wetting.
  • the autolyophobic solvent means a solvent in which the critical surface tension ⁇ C of the adsorption film of the solvent molecules themselves is smaller than the surface tension of the solvent, but even when the solvent itself has no autolyophobic properties, the lyophobic state can be obtained in the case that the ⁇ C of an adsorption monolayer of solute molecules dissolved in the solvent is smaller than the surface tension ⁇ 1V of this solvent.
  • dyes and pigments can usually be used which can be employed in writing implements or inks for coating materials.
  • the dye becomes one component of the vehicle, but the pigment does not become the component of the vehicle.
  • an inorganic pigment or an organic pigment can be directly used, and a processed pigment or a dispersed toner obtained by surface modification with a resin or a surface active agent may also be used.
  • the pigment include titanium oxide, carbon black, phthalocyanine compounds, azo compounds, anthraquinone compounds, quinacridone compounds, Microlease Color (made by Ciba-Geigy) and Fuji AS Color (made by Fuji Dyestuff Co., Ltd.).
  • Microlease Color made by Ciba-Geigy
  • Fuji AS Color made by Fuji Dyestuff Co., Ltd.
  • Typical trade manes of the coagulants include organic bentonites such as Benton SD-2 and Benton 27 made by NL Chemicals Co., Ltd., TIXOGEL VZ and TIXOGEL EZ made by Nissan Gardler Catalyst Co., Ltd., EX-0101 made by SUD Chemicals, Inc., silica compounds such as Mizcasil P-801 made by Mizusawa Chemical Industry Co., Ltd., Aerosil 380 and Aerosil COK84 made by Nippon Aerosil Co., Ltd., polyamides of fatty acids such as Tarlene VA-100, VA-500 and VA-800 made by Koeisha Oil & Fat Chemicals, Inc., ASA T-1, T-51 and T-350F made by Ito Seiyu Co., Ltd and the like.
  • the content of the coagulant is in the range of 0.01 to 10%, preferably 0.5 to 5%.
  • the generation of the blobbing phenomenon is affected by both of the autolyophobic properties (the contact angle) of the vehicle and the viscosity of the ink. Therefore, if the viscosity is 200 mPa ⁇ s or less and the contact angle is large, the blobbing phenomenon can be suppressed, but if the viscosity is more than 200 mPa ⁇ s and the contact angle is small, the blobbing phenomenon occurs.
  • the ball point pen of the present invention is constituted of a pen point comprising a ball and a tip holder, an ink reserving tube and a joint for joining the tip to the ink reserving tube, and the ink reserving tube is filled with the above-mentioned ink for the ball point pen of the present invention.
  • a material for the tip holder there can be used a material having a surface energy higher than that of the solvent for use in the non-aqueous ink, and typical examples of such a material include metals such as stainless steel and nickel silver, and ceramics having practical strength.
  • the non-aqueous ball point pen by imparting the autolyophobic properties to the ink, the non-aqueous ball point pen can be obtained in which the tip holder is scarcely wetted with the ink at the time of the rotation of the ball, so that the blobbing decreases, and simultaneously, by virtue of the autolyophobic properties of the ink, liquid molecules or the oleophobic additive is adsorbed on the surface of a solid such as a metal, and the lubricating properties are improved owing to the presence of the oriented molecules, and in consequence, the wear can be decreased, with the result that a smooth light writing feeling can be attained.
  • a spiral line was continuously written by freehand writing to observe a writing state.
  • compositions shown in Tables 1 and 2 used in the examples and the comparative examples are as follows.
  • Inks for ball point pens were prepared in blend ratios (parts by weight) shown in Table 2. Tests were carried out by the use of ball point pens filled with these inks, and the results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Pens And Brushes (AREA)

Claims (5)

  1. Nicht-wässrige Kugelschreibertinte mit einem nicht-Newtonschen Viskositätsindex von 0,2 bis 0,5 und einer Viskosität von 1000 mPa·s (25°C, 50 U/min) oder weniger, umfassend (a) ein autolyophobes Bindemittel, das ein organisches Lösungsmittel mit einem Dampfdruck von 0,2 mmHg (20°C) oder weniger, ein Pigmentdispergiermittel und bei Bedarf ein ölabweisendes Additiv umfasst und in dem ein Kontaktwinkel zur Oberfläche eines Materials wie rostfreier Stahl oder Bronze mit einer hohen freien Oberflächenenergie im Bereich von 5 bis 40° liegt, (b) ein Koagulationsmittel und (c) ein Pigment.
  2. Nicht-wässrige Kugelschreibertinte mit einem Nicht-Newtonschen Viskositätsindex von 0,2 bis 0,5 und einer Viskosität von 1000 mPa·s (25°C, 50 U/min) oder weniger, umfassend (a') ein autolyophobes Bindemittel, das ein organisches Lösungsmittel mit einem Dampfdruck von 0,2 mmHg (20°C) oder weniger, einen Farbstoff und bei Bedarf ein ölabweisendes Additiv umfasst und in dem ein Kontaktwinkel zur Oberfläche eines Materials wie rostfreier Stahl oder Bronze mit einer hohen freien Oberflächenenergie im Bereich von 5 bis 40° liegt, und (b) ein Koagulationsmittel.
  3. Nicht-wässrige Kugelschreibertinte nach Anspruch 1 oder 2, die ein Lösungsmittel mit autolyophoben Eigenschaften enthält.
  4. Nicht-wässrige Kugelschreibertinte nach Anspruch 1 oder 2, die ein Lösungsmittel ohne autolyophobe Eigenschaften und ein ölabweisendes Additiv enthält.
  5. Kugelschreiber, der eine Spitze, umfassend eine Kugel und einen Spitzenhalter, sowie ein Tintenvorratsröhrchen umfasst, wobei das Tintenvorratsröhrchen mit einer Tinte nach einem der Ansprüche 1 bis 4 gefüllt ist.
EP95114539A 1994-09-16 1995-09-15 Kugelschreiber und nicht-wässrige Tinte für Kugelschreiber Expired - Lifetime EP0702066B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP6222102A JPH0885772A (ja) 1994-09-16 1994-09-16 油性ボールペン用インキ
JP22210294 1994-09-16
JP222102/94 1994-09-16
JP7202211A JPH0948941A (ja) 1995-08-08 1995-08-08 油性ボールペンインキおよびボールペン
JP202211/95 1995-08-08
JP20221195 1995-08-08

Publications (3)

Publication Number Publication Date
EP0702066A2 EP0702066A2 (de) 1996-03-20
EP0702066A3 EP0702066A3 (de) 1997-06-18
EP0702066B1 true EP0702066B1 (de) 2001-02-28

Family

ID=26513241

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95114539A Expired - Lifetime EP0702066B1 (de) 1994-09-16 1995-09-15 Kugelschreiber und nicht-wässrige Tinte für Kugelschreiber

Country Status (7)

Country Link
US (1) US5868511A (de)
EP (1) EP0702066B1 (de)
KR (1) KR0164664B1 (de)
CN (2) CN1070524C (de)
CA (1) CA2158382C (de)
DE (1) DE69520182T2 (de)
TW (1) TW360691B (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6160035A (en) * 1996-04-15 2000-12-12 Mitsubishi Pencil Kabushiki Kaisha Oil-base pigment ink composition for writing tools
JPH1129733A (ja) * 1997-07-11 1999-02-02 Mitsubishi Pencil Co Ltd 筆記具用インキ組成物
JP3827412B2 (ja) * 1997-07-28 2006-09-27 三菱鉛筆株式会社 インキ組成物
US6224284B1 (en) 1999-10-12 2001-05-01 Dri Mark Products Incorporated Metallic ink composition for wick type writing instruments
JP3327465B2 (ja) 1999-11-18 2002-09-24 株式会社パイロット 油性ボールペン用インキ及びそのインキを用いたボールペン
JP3327466B2 (ja) 1999-11-18 2002-09-24 株式会社パイロット 水性ボールペンに近似した筆跡を形成するゲル状の油性ボールペン用インキ及びそのインキを用いたボールペン
AUPR446901A0 (en) * 2001-04-19 2001-05-17 Bottle Magic (Australia) Pty Ltd Vitreous coating
US6797748B2 (en) 2001-06-08 2004-09-28 Bic Corporation Polyurethane based inks for writing instruments
US7381754B2 (en) * 2001-07-31 2008-06-03 Mitsubishi Pencil Co., Ltd. Oil-based ink composition and uses thereof

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB738641A (en) * 1950-09-11 1955-10-19 Mentmore Mfg Co Ltd Improvements in ball-pointed writing instruments
BE534282A (de) * 1953-12-21
US2979030A (en) * 1957-02-25 1961-04-11 Parker Pen Co Writing instruments
US3030925A (en) * 1957-06-17 1962-04-24 Parker Pen Co Writing instruments
US2853972A (en) * 1957-11-08 1958-09-30 Scripto Inc Writing instrument and ink therefor
NL251732A (de) * 1959-05-19
US4077807A (en) * 1975-02-20 1978-03-07 Gordon S. Lacy Ball pen inks which do not form clogging crystalline masses within copper or copper alloy ink cartridges
US4091129A (en) * 1977-05-16 1978-05-23 Paper Converting Machine Company Method and apparatus for coating using an open-ended ink chamber having restrictions for partially limit ink flow
US4218251A (en) * 1978-08-24 1980-08-19 Minnesota Mining And Manufacturing Company Driographic ink
US4492968A (en) * 1982-09-30 1985-01-08 International Business Machines Dynamic control of nonlinear ink properties for drop-on-demand ink jet operation
US4726845A (en) * 1986-06-04 1988-02-23 Parker Pen (Benelux) B.V. Hybrid marking instrument and writing ink composition
US5000786A (en) * 1987-11-02 1991-03-19 Seiko Epson Corporation Ink composition and ink jet recording apparatus and method
JPH06239086A (ja) * 1993-02-15 1994-08-30 Mitsubishi Pencil Co Ltd ボールペン
JPH06247091A (ja) 1993-03-01 1994-09-06 Mitsubishi Pencil Co Ltd 油性ボールペン用チップ
JP3258129B2 (ja) * 1993-04-28 2002-02-18 三菱鉛筆株式会社 油性ボールペン

Also Published As

Publication number Publication date
DE69520182D1 (de) 2001-04-05
EP0702066A3 (de) 1997-06-18
TW360691B (en) 1999-06-11
US5868511A (en) 1999-02-09
DE69520182T2 (de) 2001-08-30
CA2158382A1 (en) 1996-03-17
CN1070524C (zh) 2001-09-05
EP0702066A2 (de) 1996-03-20
CA2158382C (en) 1999-03-16
CN1130664A (zh) 1996-09-11
CN1282672A (zh) 2001-02-07
KR960010802A (ko) 1996-04-20
KR0164664B1 (ko) 1999-01-15

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